CN114289029A - Ozone catalytic oxidation composite catalyst and preparation method and application thereof - Google Patents
Ozone catalytic oxidation composite catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 48
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 33
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 24
- 239000002351 wastewater Substances 0.000 claims abstract description 20
- 238000004939 coking Methods 0.000 claims abstract description 18
- 238000011068 loading method Methods 0.000 claims abstract description 13
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- 238000000034 method Methods 0.000 claims description 29
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- 230000000694 effects Effects 0.000 description 5
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
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- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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Abstract
The invention discloses an ozone catalytic oxidation composite catalyst, which comprises: carrier, active component and adjuvant, the carrier packageIncluding gamma-Al2O3The active components are oxides of Fe, Cu and Ni, and the auxiliary agent is Ce oxide. In the active component, the mass ratio of Fe, Cu and Ni oxide is 1:1.5-6: 1.5-6; the mass of the auxiliary agent Ce oxide is 25-85% of that of the active component Fe oxide; the loading amount of the active component metal oxide is 5-10% by the total mass of the catalyst. The ozone catalytic oxidation catalyst provided by the invention has the advantages of easily available raw materials, low cost and simple preparation method, can effectively treat high-concentration coking wastewater, and can achieve a COD removal rate as high as 83%.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to an ozone catalytic oxidation composite catalyst, a preparation method of the ozone catalytic oxidation composite catalyst, and further relates to an application of the ozone catalytic oxidation composite catalyst.
Background
At present, the ozone catalyst mainly comprises minerals, metal (hydrogen) oxides, metal oxide supported catalysts, modified solid waste catalysts and the like, and the appearance form of the ozone catalyst mainly comprises a spherical shape, a granular shape, a powdery shape, a honeycomb shape, an amorphous shape and the like. Among them, the spherical supported catalyst is attracting much attention due to its advantages of high catalytic efficiency, high strength, easy preparation, stable effect and the like, and can be applied to industrial wastewater treatment.
The coking wastewater is wastewater generated in the processes of high-temperature cracking and dry distillation of raw coal, gas purification and refining of chemical products, and is high-concentration refractory organic wastewater taking phenols and nitrogen heterocyclic substances as main components. The coking wastewater is mixed sewage from each process section, has complex and variable components and high toxicity, and contains more substances which are difficult to biodegrade, such as phenol, cyanogen, aliphatic compounds, heterocyclic compounds, polycyclic compounds and the like. In addition to organics, there are a number of inorganic components such as sulfides, cyanides, ammonia nitrogen, and the like. In the coking wastewater, the phenolic compound is a prototype poison, has a certain poisoning effect on all organisms, can make the cells of the organisms lose activity, and coagulates protein. Many of polycyclic and heterocyclic compounds have carcinogenic and mutagenic effects, and people who have been exposed to coal tar, pitch, and the like for a long time have a high probability of having skin cancer, lip cancer, and lung cancer. But the coking wastewater is one of industrial wastewater which is difficult to degrade, and the effluent standard is difficult to reach by adopting a conventional biological method. Therefore, the improvement of the coking wastewater treatment technology is urgently needed.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems: advanced oxidation is a common method for wastewater treatment, particularly, the ozone catalytic oxidation technology can effectively treat industrial wastewater, but the COD of coking wastewater cannot be effectively reduced by the existing ozone catalytic oxidation catalysts, and the ozone catalytic oxidation technology needs to be improved.
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the embodiment of the invention provides an ozone catalytic oxidation composite catalyst which is simple in preparation method, easy in raw material obtaining, low in cost, capable of effectively treating high-concentration coking wastewater and capable of reaching a COD removal rate of 83%.
The ozone catalytic oxidation composite catalyst provided by the embodiment of the invention comprises: a carrier, an active component and an auxiliary agent, wherein the carrier comprises gamma-Al2O3The active components are oxides of Fe, Cu and Ni, and the auxiliary agent is an oxide of Ce.
The ozone catalytic oxidation composite catalyst provided by the embodiment of the invention has the advantages and technical effects that 1, in the embodiment of the invention, oxides of Fe, Cu and Ni are used as active components and cooperate with an oxide of an auxiliary agent Ce, and the active components and the auxiliary agent play a synergistic effect, so that the COD removal rate of high-concentration coking wastewater is effectively improved, and can reach 83%; 2. in the embodiment of the invention, the raw materials are simple and easy to obtain, the cost is low, and the preparation method is simple and is easy for large-scale industrial production.
In some embodiments, the mass ratio of the three oxides of Fe, Cu and Ni in the active component is 1:1.5-6: 1.5-6.
In some embodiments, the mass ratio of the three oxides of Fe, Cu and Ni in the active component is 1:4.5: 4.5.
In some embodiments, the mass of the promoter Ce oxide is 25-85% of the mass of the active component Fe oxide.
In some embodiments, the mass of the promoter Ce oxide is 50% of the mass of the active component Fe oxide.
In some embodiments, the loading of the active component metal oxide is 5-10% by mass of the total mass of the catalyst.
The embodiment of the invention also provides a preparation method of the ozone catalytic oxidation composite catalyst, which comprises the following steps:
a. mixing salt solutions of active components Fe, Cu and Ni with a salt solution of an auxiliary agent Ce to obtain an impregnation solution;
b. adding a carrier into a granulator, spraying the impregnation liquid on the carrier, and granulating to obtain small balls;
c. and drying and roasting the pellets to prepare the spherical catalyst.
The preparation method of the ozone catalytic oxidation composite catalyst provided by the embodiment of the invention brings advantages and technical effects, 1, in the method provided by the embodiment of the invention, the catalyst is prepared by adopting a pelletizing method, powder particles are agglomerated together under the action of a liquid bridge and capillary force to form a micronucleus, and under the action of friction force and rolling impact generated by rotation of a container, the micronucleus continuously rotates and grows in a powder layer to finally form spherical particles with a certain size; the pelletizing method has the advantages of large treatment capacity, small equipment investment, high running rate and the like; 2. in the method of the embodiment of the invention, Fe, Cu and Ni oxides are used as active components and cooperate with an auxiliary agent Ce oxide, and the active components and the auxiliary agent play a synergistic role, so that the COD removal rate of the high-concentration coking wastewater is effectively improved; 3. in the method provided by the embodiment of the invention, the raw materials are simple and easy to obtain, the cost is low, and the preparation method is simple and is easy for large-scale industrial production.
In some embodiments, in the step c, the calcination temperature is 500-600 ℃, and the calcination time is 3-5 h.
In some embodiments, in step c, the spherical catalyst has a particle size of 3 to 5 mm.
The embodiment of the invention also provides application of the ozone catalytic oxidation composite catalyst or the composite catalyst prepared by the preparation method in the embodiment of the invention in coking wastewater.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and not to be construed as limiting the invention.
The ozone catalytic oxidation composite catalyst provided by the embodiment of the invention comprises: a carrier, an active component and an auxiliary agent, wherein the carrier comprises gamma-Al2O3The active components are oxides of Fe, Cu and Ni, and the auxiliary agent is Ce oxide.
According to the ozone catalytic oxidation composite catalyst provided by the embodiment of the invention, oxides of Fe, Cu and Ni are used as active components and cooperate with an auxiliary agent Ce oxide, and the active components and the auxiliary agent play a synergistic role, so that the COD removal rate of high-concentration coking wastewater is effectively improved; in the embodiment of the invention, the raw materials are simple and easy to obtain, the cost is low, and the preparation method is simple and is easy for large-scale industrial production.
In some embodiments, in the active component, the mass ratio of Fe, Cu and Ni oxides is preferably 1:1.5-6:1.5-6, and more preferably 1:4.5: 4.5; the mass of the assistant Ce oxide is preferably 25-85%, and more preferably 50% of the mass of the active component Fe oxide. In the embodiment of the invention, the proportion of the active component and the auxiliary agent is optimized, the performance of the catalyst is further improved, the metal loss rate is high due to the overhigh content of the Fe oxide in the active component, and the performance of the catalyst is reduced due to the overlow content of the Fe oxide in the active component. If the amount of the auxiliary Ce oxide in the catalyst is too much, the cost of the catalyst is increased, and meanwhile, the performance of the catalyst is reduced due to the fact that the amount of the Ce oxide is too much or too little.
In some embodiments, the loading amount of the active component metal element is preferably 5 to 10%, and more preferably 8%, based on the total mass of the catalyst. In the embodiment of the invention, the loading of the active component is optimized, the loading is too low, the active component of the catalyst is too little, the COD removal rate of coking wastewater is low, if the loading is too high, the active sites on the surface of the catalyst are covered, and the metal particles enter the pores in the carrier to block the pore channels, so that the specific surface area and the pore volume are reduced, and the performance of the catalyst is reduced.
The embodiment of the invention also provides a preparation method of the ozone catalytic oxidation composite catalyst, which comprises the following steps:
a. mixing salt solutions of active components Fe, Cu and Ni with a salt solution of an auxiliary agent Ce to obtain an impregnation solution;
b. adding a carrier into a granulator, spraying the impregnation liquid on the carrier, and granulating to obtain small balls;
c. and drying and roasting the pellets to prepare the spherical catalyst.
According to the preparation method of the ozone catalytic oxidation composite catalyst, a pelletizing method is adopted to prepare the catalyst, powder particles are agglomerated together under the action of a liquid bridge and capillary force to form micro-cores, and the micro-cores continuously rotate and grow in a powder layer under the action of friction force and rolling impact generated by rotation of a container to finally form spherical particles with a certain size; the pelletizing method has the advantages of large treatment capacity, small equipment investment, high running rate and the like; in the method of the embodiment of the invention, Fe, Cu and Ni oxides are used as active components and cooperate with an auxiliary agent Ce oxide, and the active components and the auxiliary agent play a synergistic role, so that the COD removal rate of the high-concentration coking wastewater is effectively improved; in the method provided by the embodiment of the invention, the raw materials are simple and easy to obtain, the cost is low, and the preparation method is simple and is easy for large-scale industrial production.
In some embodiments, the calcination temperature in step c is preferably 500-. In the method of the embodiment of the invention, the roasting temperature and time are optimized, and if the temperature is too low or the roasting time is too short, the roasting time is within gamma-Al2O3The surface active component and the auxiliary agent can not completely form metal oxide with good crystal form and high activity, the catalytic performance is poor, if the temperature is too high or the roasting time is too long, the surface of the catalyst can be sintered or partially sintered, so that the surface active sites of the catalyst are lost or reduced, and the performance of the catalyst is reduced in the catalytic ozonation process.
In some embodiments, in step c, the spherical catalyst preferably has a particle size of 3 to 5 mm. In the embodiment of the invention, the particle size of the catalyst is optimized, and the performance of the catalyst can be further improved.
The embodiment of the invention also provides application of the ozone catalytic oxidation composite catalyst or the composite catalyst prepared by the preparation method in the embodiment of the invention in coking wastewater.
The present invention will be described in detail with reference to examples.
Example 1
Adding water into ferric nitrate, cupric nitrate, nickel nitrate and cerous nitrate, mixing to form impregnation liquid, and adding a carrier gamma-Al into a granulator in small amount for multiple times2O3Simultaneously spraying the impregnation liquid on the carrier to fully mix the components of the carrier and the impregnation liquid, slowly growing into balls, screening out 3-5mm small balls, developing for 24h, and drying and roasting at 500 ℃ for 4h to prepare the spherical catalyst.
In the spherical catalyst prepared in the embodiment, the total loading of the active components Fe, Cu and Ni oxides is 5%, and the mass ratio of the Fe, Cu, Ni and Ce oxides is 1:2:2: 0.5.
And (3) testing the stability of the catalyst: soaking the catalyst in a simulated water sample, wherein the simulated water sample consists of quinoline, nitrobenzene, hydroquinone, isoamyl glycol, n-heptane and the like, the COD value is about 240mg/L, placing the simulated water sample in a shaking table to vibrate, and then measuring the concentration of metal ions in water, and the result is shown in table 1.
TABLE 1
| Reactive metal | 24h/mg/L | 48h/mg/L | 72h/mg/L | 96h/mg/L | 120h/mg/L |
| Cu | 0 | 0 | 0 | 0 | 0 |
| Fe | 0 | 0 | 0 | 0 | 0 |
| Ni | 0 | 0 | 0 | 0 | 0 |
| Ce | 0.12 | 0.10 | 0.09 | 0.13 | 0.11 |
After the catalyst prepared by the embodiment is soaked and vibrated for 24-120h with a simulated water sample, active components Cu, Fe and Ni are very stable and are not dissolved out; the auxiliary agent Ce is slightly dissolved out.
And (3) testing the catalytic performance: the spherical catalyst prepared by the embodiment is used for carrying out ozone catalytic oxidation treatment on coking wastewater, and COD in the coking wastewater is as follows: 300mg/L, and the main components comprise: quinoline, phenol, dimethylphenol, naphthalene, dibenzofuran, benzocyclohexene, and the like. The reaction apparatus was a glass column (internal diameter 4cm, height 1.5m) and the wastewater was circulated by a peristaltic pump for uniform mixing. Controlling outlet O of ozone generator3Gas flow rate of 0.2L/min, O3The gas concentration was 80mg/L, and the COD concentration was analyzed by sampling at intervals, and the treatment results are shown in Table 6.
Example 2
The same procedure as in example 1 was conducted except that the spherical catalyst was produced in which the total loading of the active components of Fe, Cu and Ni oxides was 6%.
The catalyst prepared in this example was tested for catalytic performance as shown in Table 6.
Example 3
The same procedure as in example 1 was conducted except that the spherical catalyst was produced in which the total loading of the active components of Fe, Cu and Ni oxides was 8%.
The catalyst prepared in this example was tested for catalytic performance as shown in Table 6.
Example 4
The same procedure as in example 1 was conducted except that the spherical catalyst was produced in which the total loading of the active components of Fe, Cu and Ni oxides was 10%.
The catalyst prepared in this example was tested for catalytic performance as shown in Table 6.
Example 5
The same procedure as in example 1 was repeated, except that the catalyst was prepared such that the mass ratio of the oxides of Fe, Cu, Ni and Ce was 1:2:2: 0.25.
The catalyst prepared in this example was tested for catalytic performance as shown in Table 6.
Example 6
The same as in example 1 except that the mass ratio of Fe, Cu, Ni and Ce oxides in the prepared catalyst was 1:4.5:4.5: 0.5.
The catalyst prepared in this example was tested for catalytic performance as shown in Table 6.
Example 7
The same as in example 1 except that the mass ratio of Fe, Cu, Ni and Ce oxides in the prepared catalyst was 1:6:6: 0.5.
The catalyst prepared in this example was tested for catalytic performance as shown in Table 6.
Example 8
The same procedure as in example 1 except that pellets of 6 to 8mm were selected and calcined after being pelletized by a pelletizer.
The catalyst prepared in this example was tested for catalytic performance as shown in Table 6.
Example 9
The same procedure as in example 1 was repeated, except that after the granulation by the granulator, pellets of 1 to 2mm were selected and calcined.
The catalyst prepared in this example was tested for catalytic performance as shown in Table 6.
Example 10
The same procedure as in example 1 was repeated, except that the catalyst was prepared such that the mass ratio of the oxides of Fe, Cu, Ni and Ce was 1:2:2: 0.85.
The catalyst prepared in this example was tested for catalytic performance as shown in Table 6.
Comparative example 1
The same procedure as in example 1, except that the auxiliary agent of the catalyst was magnesium oxide, and iron nitrate, copper nitrate, nickel nitrate, and magnesium nitrate were mixed with water to form an impregnation solution, to obtain a catalyst in which the mass ratio of Fe, Cu, Ni, and Mg oxides was 1:2:2: 0.5.
The results of the stability test of the catalyst prepared in comparative example 1 are shown in Table 2.
TABLE 2
| Reactive metal | 24h/mg/L | 48h/mg/L | 72h/mg/L | 96h/mg/L | 120h/mg/L |
| Cu | 0 | 0 | 0 | 0 | 0 |
| Fe | 0 | 0 | 0 | 0 | 0 |
| Ni | 0 | 0 | 0 | 0 | 0 |
| Mg | 0.38 | 0.51 | 0.35 | 0.29 | 0.21 |
The catalyst prepared in comparative example 1 was tested for catalytic performance as shown in table 6.
Comparative example 2
The same procedure as in example 1, except that the assistant of the catalyst was calcium oxide, and iron nitrate, copper nitrate, nickel nitrate, and calcium nitrate were mixed with water to form an impregnation solution, and the mass ratio of Fe, Cu, Ni, and Ca oxides in the catalyst was 1:2:2: 0.5.
The results of the stability test of the catalyst prepared in comparative example 2 are shown in Table 3.
TABLE 3
| Reactive metal | 24h/mg/L | 48h/mg/L | 72h/mg/L | 96h/mg/L | 120h/mg/L |
| Cu | 0 | 0 | 0 | 0 | 0 |
| Fe | 0 | 0 | 0 | 0 | 0 |
| Ni | 0 | 0 | 0 | 0 | 0 |
| Ca | 75.81 | 86.82 | 83.35 | 79.55 | 77.04 |
The catalyst prepared in comparative example 2 was tested for catalytic performance as shown in table 6.
Comparative example 3
The same procedure as in example 1 was repeated, except that the active components of the catalyst were metal oxides of Fe, Cu and Mn, and iron nitrate, copper nitrate, manganese nitrate and cobalt nitrate were mixed with water to form an impregnation solution, and the mass ratio of the oxides of Fe, Cu, Mn and Ce in the catalyst was 1:2:2: 0.5.
The catalyst stability test results are shown in table 4.
TABLE 4
| Reactive metal | 24h/mg/L | 48h/mg/L | 72h/mg/L | 96h/mg/L | 120h/mg/L |
| Cu | 0 | 0 | 0 | 0 | 0 |
| Fe | 0 | 0 | 0 | 0 | 0 |
| Mn | 0.39 | 0.38 | 0.45 | 0.64 | 0.55 |
| Ce | 0.13 | 0.11 | 0.1 | 0.1 | 0.09 |
The results of the catalytic performance test of the catalyst prepared in comparative example 3 are shown in Table 6.
Comparative example 4
The same procedure as in example 1 was repeated, except that the catalyst was prepared such that the mass ratio of the oxides of Fe, Cu, Ni and Ce was 1:1:1: 0.5.
The results of the catalytic performance test of the catalyst prepared in comparative example 4 are shown in Table 6.
Comparative example 5
The same procedure as in example 1 was repeated, except that the catalyst was obtained without adding the auxiliary element, in which the total loading of the active components Fe, Cu and Ni oxides was 5.5%.
The catalyst obtained in comparative example 8 was tested for catalytic performance as shown in Table 6.
The carrier, active component, auxiliary agent, loading amount, and catalyst particle size of the catalysts prepared in examples 1 to 10 and comparative examples 1 to 5 are shown in Table 5.
TABLE 5
TABLE 6
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. An ozone catalytic oxidation composite catalyst, comprising: a carrier, an active component and an auxiliary agent, wherein the carrier comprises gamma-Al2O3The active components are oxides of Fe, Cu and Ni, and the auxiliary agent is Ce oxide.
2. The ozone catalytic oxidation composite catalyst as claimed in claim 1, wherein the mass ratio of the three oxides of Fe, Cu and Ni in the active component is 1:1.5-6: 1.5-6.
3. The ozone catalytic oxidation composite catalyst as claimed in claim 1, wherein the active component comprises three oxides of Fe, Cu and Ni in a mass ratio of 1:4.5: 4.5.
4. The ozone catalytic oxidation composite catalyst as claimed in claim 1, wherein the mass of the auxiliary Ce oxide is 25-85% of the mass of the active component Fe oxide.
5. The ozone catalytic oxidation composite catalyst as claimed in claim 1, wherein the mass of the auxiliary Ce oxide is 50% of the mass of the active component Fe oxide.
6. The catalytic ozonation composite catalyst of claim 1, wherein the loading amount of the active component metal oxide is 5-10% by total mass of the catalyst.
7. The method for preparing the ozone catalytic oxidation composite catalyst according to any one of claims 1 to 6, characterized by comprising the steps of:
a. mixing salt solutions of active components Fe, Cu and Ni with a salt solution of an auxiliary agent Ce to obtain an impregnation solution;
b. adding a carrier into a granulator, spraying the impregnation liquid on the carrier, and granulating to obtain small balls;
c. and drying and roasting the pellets to prepare the spherical catalyst.
8. The method as claimed in claim 7, wherein the calcination temperature in step c is 500-600 ℃ and the calcination time is 3-5 h.
9. The method according to claim 7, wherein the spherical catalyst has a particle size of 3 to 5mm in the step c.
10. Use of the ozone catalytic oxidation composite catalyst according to any one of claims 1 to 6 or the composite catalyst prepared by the preparation method according to any one of claims 7 to 9 in coking wastewater.
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